TWI690575B - 電子零件構裝用接著劑及倒裝晶片構裝用接著膜 - Google Patents

電子零件構裝用接著劑及倒裝晶片構裝用接著膜 Download PDF

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TWI690575B
TWI690575B TW104106575A TW104106575A TWI690575B TW I690575 B TWI690575 B TW I690575B TW 104106575 A TW104106575 A TW 104106575A TW 104106575 A TW104106575 A TW 104106575A TW I690575 B TWI690575 B TW I690575B
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meth
adhesive
group
acrylate
electronic parts
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TW104106575A
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TW201538657A (zh
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脇岡紗香
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日商積水化學工業股份有限公司
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

本發明之目的在於提供一種可於較短之構裝時間內抑制焊料流動且充分進行焊接、抑制空隙、耐回焊性亦優異之電子零件構裝用接著劑。又，本發明之目的在於提供一種含有該電子零件構裝用接著劑之倒裝晶片構裝用接著膜。本發明之電子零件構裝用接著劑含有：側鏈具有(甲基)丙烯醯基之雙鍵當量1~5meq/g之丙烯酸聚合物、3官能以上之多官能(甲基)丙烯酸酯化合物、及自由基聚合起始劑。

Description

電子零件構裝用接著劑及倒裝晶片構裝用接著膜
本發明係關於一種可於較短之構裝時間內抑制焊料流動且充分進行焊接、抑制空隙、耐回焊性亦優異之電子零件構裝用接著劑。又，本發明係關於一種含有該電子零件構裝用接著劑之倒裝晶片構裝用接著膜。
近年，為了應對逐漸發展之半導體裝置之小型化、高積體化，使用具有由焊料等構成之突起電極(凸塊)之半導體晶片之倒裝晶片構裝受到關注。
於倒裝晶片構裝中，通常使用如下方法：將半導體晶片之突起電極與其他半導體晶片或基板之電極接合後，注入底膠而進行樹脂密封(例如，專利文獻1)。
然而，近年，於半導體晶片之小型化進行之同時，電極間之間距亦逐漸變窄，又，伴隨該等情況，半導體晶片彼此或半導體晶片與基板間之間隙變窄，因此於注入底膠時會夾帶空氣，而變得容易產生空隙(void)。
因此，使用如下方法而非於電極接合後注入底膠，即，預先對基板或半導體晶片供給熱硬化型接著劑或接著膜，藉由加熱同時進行電 極接合與接著劑之硬化，從而構裝半導體晶片(例如，專利文獻2)。
然而，於此種方法中，若接著劑之硬化較慢，則存在於焊料熔融時接著劑並未充分硬化，熔融之焊料因接著劑之流動而被擠壓流動(焊料流動)之情況。又，若於構裝時接著劑並未充分硬化，則於構裝後之冷卻過程中變得容易產生空隙。於倒裝晶片構裝中，為了提高生產性，亦要求縮短構裝時間，但先前之接著劑或接著膜難以於較短之構裝時間內抑制焊料流動且充分進行焊接。
[先前技術文獻]
[專利文獻]
專利文獻1：日本特開2010-278334號公報
專利文獻2：日本特開2011-29392號公報
本發明之目的在於提供一種可於較短之構裝時間內抑制焊料流動且充分進行焊接、抑制空隙、耐回焊性亦優異之電子零件構裝用接著劑。又，本發明之目的在於提供一種含有該電子零件構裝用接著劑之倒裝晶片構裝用接著膜。
本發明係含有：側鏈具有(甲基)丙烯醯基之雙鍵當量1~5meq/g之丙烯酸聚合物、3官能以上之多官能(甲基)丙烯酸酯化合物、及自由基聚合起始劑之電子零件構裝用接著劑。
以下對本發明進行詳細說明。
本發明者以於較短之構裝時間內抑制焊料流動且充分進行焊接為目的，對藉由自由基聚合反應而硬化之含有側鏈具有(甲基)丙烯醯基之丙烯酸聚合物之電子零件構裝用接著劑進行研究。
迄今為止，已知有例如含有丙烯酸聚合物之接著劑組成物(日本特開2010-126617號公報)、含有二烯系化合物之聚合物或共聚物中兩末端具有可聚合之碳-碳雙鍵之化合物之樹脂組成物(日本專利第5228419號公報)等，但該等組成物旨在維持電子零件之接著時之接合可靠性(例如耐熱性、耐濕熱穩定性等)，於倒裝晶片構裝中難以在較短之構裝時間內抑制焊料流動且充分進行焊接。
與此相對，本發明者發現，若為含有側鏈具有(甲基)丙烯醯基之雙鍵當量1~5meq/g之丙烯酸聚合物、3官能以上之多官能(甲基)丙烯酸酯化合物、及自由基聚合起始劑之電子零件構裝用接著劑，則可於較短之構裝時間內抑制焊料流動且充分進行焊接，抑制空隙，耐回焊性亦優異，從而完成本發明。
本發明之電子零件構裝用接著劑含有：側鏈具有(甲基)丙烯醯基之雙鍵當量1~5meq/g之丙烯酸聚合物(以下亦簡稱為「側鏈具有(甲基)丙烯醯基之丙烯酸聚合物」)、3官能以上之多官能(甲基)丙烯酸酯化合物、及自由基聚合起始劑。
藉由含有該等成分，本發明之電子零件構裝用接著劑成為藉由自由基聚合反應而硬化，可於較短之構裝時間內抑制焊料流動且充分進行焊接者，又，可於構裝時充分硬化，而抑制於構裝後之冷卻過程中產生空隙。 又，本發明之電子零件構裝用接著劑成為接合可靠性亦優異者，耐回焊性提高。
上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物只要於側鏈具有(甲基)丙烯醯基，則並無特別限定，較佳為僅側鏈具有(甲基)丙烯醯基。
再者，所謂側鏈具有(甲基)丙烯醯基意指並非於最長之碳鏈即「主鏈」之單末端或兩末端，而係自主鏈分支之「側鏈」中具有(甲基)丙烯醯基。
上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物之雙鍵當量的下限為1meq/g，上限為5meq/g。若上述雙鍵當量未達1meq/g，則變得容易產生焊料流動，焊接性降低，又，於構裝後之冷卻過程變得容易產生空隙。再者，側鏈具有(甲基)丙烯醯基之雙鍵當量超過5meq/g之丙烯酸聚合物於合成時之聚合或反應時容易凝膠化，因此合成本身較難。上述雙鍵當量之較佳之下限為1.1meq/g，較佳之上限為4.5meq/g，更佳之下限為1.2meq/g，更佳之上限為4meq/g。
再者，本說明書中之所謂雙鍵當量意指關於側鏈具有(甲基)丙烯醯基之丙烯酸聚合物每1g之(甲基)丙烯醯基的平均個數之指標，具體而言，可由下述式(a)而算出。
雙鍵當量(meq/g)=[側鏈具有(甲基)丙烯醯基之丙烯酸聚合物1分子中之(甲基)丙烯醯基之平均個數]×1000/[側鏈具有(甲基)丙烯醯基之丙烯酸聚合物之數量平均分子量] (a)
再者，雙鍵當量可藉由測定碘值而算出。
上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物較佳為使含 官能基之丙烯酸聚合物與可與該官能基反應且具有(甲基)丙烯醯基之化合物進行反應而得之聚合物。
再者，無需含官能基之丙烯酸聚合物之全部官能基均與可與該官能基反應、且具有(甲基)丙烯醯基之化合物反應。
上述含官能基之丙烯酸聚合物例如可使含有含官能基之(甲基)丙烯酸單體之單體混合物聚合或共聚合而得。此時之聚合方法並無特別限定，例如可列舉溶液聚合(沸點聚合或恆溫聚合)、乳化聚合、懸浮聚合、塊狀聚合等先前公知之方法。
上述含官能基之(甲基)丙烯酸單體並無特別限定，例如可列舉：(甲基)丙烯酸4-羥基丁酯、單(甲基)丙烯酸甘油酯、1,6-己二醇(甲基)丙烯酸酯、(甲基)丙烯酸羥基乙酯、聚丙二醇單(甲基)丙烯酸酯等含羥基之(甲基)丙烯酸單體；N-甲基(甲基)丙烯醯胺等含醯胺基之(甲基)丙烯酸單體；異氰酸(甲基)丙烯醯氧基乙酯、異氰酸間異丙烯基-α,α-二甲基苄酯、(甲基)丙烯醯基異氰酸酯、異氰酸烯丙酯等含異氰酸酯基之(甲基)丙烯酸單體；(甲基)丙烯酸環氧丙酯等含環氧基之(甲基)丙烯酸單體；(甲基)丙烯酸等含羧基之(甲基)丙烯酸單體；(甲基)丙烯酸胺基乙酯等含胺基之(甲基)丙烯酸單體等。該等含官能基之(甲基)丙烯酸單體可單獨使用，亦可併用兩種以上。
上述單體混合物除了含有上述含官能基之(甲基)丙烯酸單體以外，例如亦可含有如下單體：N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、N-丙烯醯基嗎福啉、丙烯腈、苯乙烯、乙酸乙烯酯等乙烯基化合物；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲 基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯等(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸四氫糠酯等。該等單體可單獨使用，亦可併用兩種以上。
作為可與上述官能基反應、且具有(甲基)丙烯醯基之化合物，例如可列舉具有羧基、羥基、環氧基、胺基、異氰酸酯基、醯胺基等官能基、且具有(甲基)丙烯醯基之化合物。具體而言，例如可列舉如下之(1)~(5)之情形。
(1)對於含羥基之丙烯酸聚合物，使其與具有選自由醯胺基、異氰酸酯基、環氧基及羧基所組成之群中之至少一種、且具有(甲基)丙烯醯基之化合物反應即可。
(2)對於含羧基之丙烯酸聚合物，使其與具有環氧基或異氰酸酯基、且具有(甲基)丙烯醯基之化合物反應即可。
(3)對於含環氧基之丙烯酸聚合物，使其與具有羧基或醯胺基、且具有(甲基)丙烯醯基之化合物反應即可。
(4)對於含胺基之丙烯酸聚合物，使其與具有環氧基、且具有(甲基)丙烯醯基之化合物反應即可。
(5)對於含異氰酸酯基之丙烯酸聚合物，使其與具有羥基或羧基、且具有(甲基)丙烯醯基之化合物反應即可。
上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物之重量平均分子量(Mw)並無特別限定，較佳之下限為1萬，較佳之上限為100萬。 若上述重量平均分子量未達1萬，則存在電子零件構裝用接著劑之硬化物變脆、耐回焊性降低之情況。若上述重量平均分子量超過100萬，則存在電子零件構裝用接著劑之黏度變得過高，製膜性降低，或於構裝時變得容易引起樹脂(接著劑)嵌入焊接部之情況。上述重量平均分子量之更佳之下限為10萬，更佳之上限為80萬。
再者，重量平均分子量(Mw)可藉由凝膠滲透層析(GPC)法，作為聚苯乙烯換算分子量而測定。具體而言，關於重量平均分子量(Mw)，可藉由四氫呋喃(THF)將丙烯酸聚合物稀釋50倍，藉由過濾器過濾所得之稀釋液，使用所得之濾液並藉由GPC法作為聚苯乙烯換算分子量而測定。於GPC法中，例如可使用2690 Separations Model(Waters公司製造)等。
作為上述3官能以上之多官能(甲基)丙烯酸酯化合物，例如可列舉：乙氧化異三聚氰酸三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯等3官能化合物；二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯等4官能化合物；二新戊四醇五(甲基)丙烯酸酯等5官能化合物；二新戊四醇六(甲基)丙烯酸酯等6官能化合物；其他3官能以上之多官能(甲基)丙烯酸酯化合物、多官能(甲基)丙烯酸胺酯化合物及多官能聚酯(甲基)丙烯酸酯化合物等。該等3官能以上之多官能(甲基)丙烯酸酯化合物可單獨使用，亦可併用兩種以上。其中，就對由矽等所構成之半導體晶圓或晶片之接著力較高，即便於回焊等嚴酷之熱濕條件下亦不會產生與半導體晶圓或晶片之接著界面處之剝離或封裝龜裂之方面而言，尤佳為乙氧化異三聚氰酸三(甲基)丙烯酸酯。再者，3官能以上之多官 能(甲基)丙烯酸酯化合物係1分子中具有3個以上(甲基)丙烯酸酯部分之化合物。若1分子中(甲基)丙烯酸酯部分為2個以下，則變得容易產生焊料流動，焊接性降低，又，於構裝後之冷卻過程中變得容易產生空隙。又，本說明書中，1分子中具有(甲基)丙烯酸酯部分、以及環氧基之化合物不包括於「3官能以上之多官能(甲基)丙烯酸酯化合物」中，而將其設為下文所述之「環氧樹脂」。
上述3官能以上之多官能(甲基)丙烯酸酯化合物之含量並無特別限定，相對於上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物100重量份之較佳之下限為20重量份，較佳之上限為300重量份。若上述含量未達20重量份，則存在如下情況：變得容易產生焊料流動，焊接性降低，又，於構裝後之冷卻過程中變得容易產生空隙。若上述含量超過300重量份，則電子零件構裝用接著劑之黏性變強，例如於製成接著膜之情形時存在如下情況：於將用以在使用之前保護接著劑層而積層於接著劑層之附有脫模劑之基材剝離時會產生不良情況。又，於拾取經單片化之附有接著劑層之半導體晶片而構裝於基板或其他半導體晶片時之拾取步驟中，存在接著劑層附著於載置台上而導致拾取不良之情況。上述含量之更佳之下限為25重量份，更佳之上限為250重量份。
上述自由基聚合起始劑並無特別限定，可使用自由基聚合中通常使用之聚合起始劑，較佳為熱自由基聚合起始劑。作為上述熱自由基聚合起始劑，例如可列舉偶氮化合物、過氧化物等。該等熱自由基聚合起始劑可單獨使用，亦可併用兩種以上。再者，於偶氮化合物之情形時，由於存在反應時氮氣作為釋氣而產生，並以空隙之形式殘存於硬化物中之情 況，因此更佳為使用過氧化物。
作為上述偶氮化合物，例如可列舉：2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、1,1-偶氮雙(環己烷-1-甲腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、4,4'-偶氮雙(4-氰基戊酸)、2,2'-偶氮雙(2-甲基丙酸)二甲酯、1,1'-偶氮雙(1-環己烷羧酸)二甲酯、2,2'-偶氮雙{2-甲基-N-[1,1'-雙(羥基甲基)-2-羥基乙基]丙醯胺}、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]、2,2'-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺]、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2'-偶氮雙(N-環己基-2-甲基丙醯胺)、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙{2-[1-(2-羥基乙基)-2-咪唑啉-2-基]丙烷}二鹽酸鹽、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[N-(2-羧基乙基)-2-甲基丙脒]四水合物、2,2'-偶氮雙(1-亞胺基-1-吡咯烷基-2-甲基丙烷)二鹽酸鹽、2,2'-偶氮雙(2,4,4-三甲基戊烷)等。該等偶氮化合物可單獨使用，亦可併用兩種以上。
上述過氧化物並無特別限定，較佳為10小時半衰期溫度為80℃以上且未達140℃。若上述10小時半衰期溫度未達80℃，則由於在焊料熔融前進行電子零件構裝用接著劑之硬化，因此，存在於構裝時容易引起樹脂(接著劑)嵌入焊接部，導致接合可靠性降低之情況。若上述10小時半衰期溫度為140℃以上，則存在產生焊料流動之情況。上述10小時半衰期溫度更佳為90℃以上且未達130℃。
作為上述過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、二烷基過氧化物、二醯基過氧化物、過氧化酯、過氧化二碳酸酯 等。又，上述過氧化物中，作為有機過氧化物之市售品，例如可列舉：PEROYL 355(10小時半衰期溫度：59.4℃)、PEROYL L(10小時半衰期溫度：61.6℃)、PEROCTA O(10小時半衰期溫度：65.3℃)、PEROYL SA(10小時半衰期溫度：65.9℃)、PERHEXA 250(10小時半衰期溫度：66.2℃)、PERHEXYL O(10小時半衰期溫度：69.9℃)、NYPER PMB(10小時半衰期溫度：70.6℃)、PERBUTYL O(10小時半衰期溫度：72.1℃)、NYPER BMT(10小時半衰期溫度：73.1℃)、NYPER BW(10小時半衰期溫度：73.6℃)、PERHEXA MC(10小時半衰期溫度：83.2℃)、PERHEXA TMH(10小時半衰期溫度：86.7℃)、PERHEXA HC(10小時半衰期溫度：87.1℃)、PERHEXA C(10小時半衰期溫度：90.7℃)、PERTETRA A(10小時半衰期溫度：94.7℃)、PERHEXYL I(10小時半衰期溫度：95.0℃)、PERBUTYL MA(10小時半衰期溫度：96.1℃)、PERBUTYL 355(10小時半衰期溫度：97.1℃)、PERBUTYL L(10小時半衰期溫度：98.3℃)、PERBUTYL I(10小時半衰期溫度：98.7℃)、PERBUTYL E(10小時半衰期溫度：99.0℃)、PERHEXYL Z(10小時半衰期溫度：99.4℃)、PERHEXA 25Z(10小時半衰期溫度：99.7℃)、PERBUTYL A(10小時半衰期溫度：101.9℃)、PERHEXA 22(10小時半衰期溫度：103.1℃)、PERBUTYL Z(10小時半衰期溫度：104.3℃)、PERHEXA V(10小時半衰期溫度：104.5℃)、PERBUTYL D(10小時半衰期溫度：123.7℃)、PERCUMYL D(10小時半衰期溫度：116.4℃)、PERHEXINE 25B(10小時半衰期溫度：128.4℃)(以上為日油公司製造)等。
該等過氧化物可單獨使用，亦可併用兩種以上。
上述自由基聚合起始劑之含量並無特別限定，相對於上述側 鏈具有(甲基)丙烯醯基之丙烯酸聚合物100重量份之較佳之下限為0.5重量份，較佳之上限為20重量份。若上述含量未達0.5重量份，則存在產生焊料流動之情況。即便上述含量超過20重量份，亦不會對電子零件構裝用接著劑之硬化性產生助益。上述含量之更佳之下限為1重量份，更佳之上限為15重量份。
本發明之電子零件構裝用接著劑較佳為進而含有環氧樹脂、與環氧硬化劑。藉由含有該等成分，電子零件構裝用接著劑之接合可靠性及耐熱性變得更高，耐回焊性提高。
上述環氧樹脂並無特別限定，就可被取入於上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物與上述3官能以上之多官能(甲基)丙烯酸酯化合物之反應系統之方面而言，較佳為含有1分子中具有環氧基與(甲基)丙烯醯基之環氧化合物。再者，本說明書中，將1分子中具有環氧基與(甲基)丙烯醯基之化合物全部視為「環氧樹脂」，於該情形時，1分子中之(甲基)丙烯醯基之個數並無特別限定。
作為上述1分子中具有環氧基與(甲基)丙烯醯基之環氧化合物，例如可列舉將通常使用之環氧樹脂之環氧基部分轉化或改質為(甲基)丙烯酸基而成之化合物等。上述通常使用之環氧樹脂並無特別限定，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂等。又，作為上述1分子中具有環氧基與(甲基)丙烯醯基之環氧化合物，亦可使用丙烯酸4-羥基丁酯環氧丙醚等。該等1分子中具有環氧基與(甲基)丙烯醯基之環氧化合物可單獨使用，亦可併用兩種以上。其中，較佳為具有下述 通式(1)所表示之結構之化合物。
Figure 104106575-A0202-12-0012-1
通式(1)中，R1、R2、R3及R4表示氫原子或甲基，m及n表示0或正整數。m及n只要為0或正整數即可，但較佳為m+n為0~15之範圍。
又，亦可併用上述1分子中具有環氧基與(甲基)丙烯醯基之環氧化合物、及雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等、二環戊二烯型環氧樹脂、萘型環氧樹脂等通常之環氧樹脂。
上述環氧樹脂之含量並無特別限定，相對於上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物100重量份之較佳之下限為5重量份，較佳之上限為300重量份。若上述含量未達5重量份，則存在電子零件構裝用接著劑之接合可靠性或耐熱性降低之情況。若上述含量超過300重量份，則存在變得容易產生焊料流動，導致焊接性降低之情況，又，存在於構裝後之冷卻過程中變得容易產生空隙之情況。上述含量之更佳之下限為10重量份，更佳之上限為200重量份。
上述環氧硬化劑並無特別限定，可根據上述環氧樹脂而適當 選擇先前公知之環氧硬化劑，例如可列舉：酸酐系硬化劑、酚系硬化劑、胺系硬化劑、雙氰胺等潛伏性硬化劑；陽離子系觸媒型硬化劑、咪唑系硬化劑、三級胺系硬化促進劑等。該等環氧硬化劑可單獨使用，亦可併用兩種以上。其中，就容易調整硬化速度、硬化物之物性等方面而言，較佳為酸酐系硬化劑，就容易控制用以調整硬化速度、硬化物之物性等之反應系統之方面而言，較佳為咪唑系硬化劑。
上述酸酐系硬化劑中，作為市售品，例如可列舉：YH-306、YH-307(以上為三菱化學公司製造，常溫(25℃)下為液狀)、YH-309(三菱化學公司製造，常溫(25℃)下為固體)等。該等酸酐系硬化劑可單獨使用，亦可併用兩種以上。
上述咪唑系硬化劑並無特別限定，例如可列舉：FUJICURE 7000、FUJICURE 7001、FUJICURE 7002(以上為T&K TOKA公司製造，常溫(25℃)下為液狀)、咪唑之1位經氰乙基保護而得之1-氰乙基-2-苯基咪唑、經異三聚氰酸保護鹼性而得之咪唑系硬化劑(商品名「2MA-OK」，四國化成工業公司製造，常溫(25℃)下為固體)、2MZ、2MZ-P、2PZ、2PZ-PW、2P4MZ、C11Z-CNS、2PZ-CNS、2PZCNS-PW、2MZ-A、2MZA-PW、C11Z-A、2E4MZ-A、2MAOK-PW、2PZ-OK、2MZ-OK、2PHZ、2PHZ-PW、2P4MHZ、2P4MHZ-PW、2E4MZ．BIS、VT、VT-OK、MAVT、MAVT-OK(以上為四國化成工業公司製造)等。該等咪唑系硬化劑可單獨使用，亦可併用兩種以上。
上述環氧硬化劑之含量並無特別限定，於使用與環氧基等量反應之環氧硬化劑之情形時，上述環氧硬化劑之含量相對於電子零件構裝用接著劑中所含之環氧基之總量之較佳之下限為60當量，較佳之上限為110 當量。若上述含量未達60當量，則存在無法使上述環氧樹脂充分硬化之情況。即便上述含量超過110當量，亦未特別有助於電子零件構裝用接著劑之硬化性，存在因過量之環氧硬化劑揮發而成為空隙之原因之情況。上述含量之更佳之下限為70當量，更佳之上限為100當量。
本發明之電子零件構裝用接著劑較佳為進而含有無機填料。藉由含有無機填料，電子零件構裝用接著劑之硬化物之機械強度及耐熱性變得更高，又，硬化物之線膨脹係數降低，接合可靠性變得更高。
上述無機填料並無特別限定，例如可列舉：二氧化矽(silica)、氧化鋁、氮化鋁、氮化硼、氮化矽、碳化矽、氧化鎂、氧化鋅等。其中，就流動性優異之方面而言，較佳為球狀二氧化矽，更佳為經甲基矽烷偶合劑、苯基矽烷偶合劑、乙烯基矽烷偶合劑、(甲基)丙烯酸矽烷偶合劑等進行表面處理之球狀二氧化矽。藉由使用經表面處理之球狀二氧化矽，可提高電子零件構裝用接著劑之製膜性。
上述無機填料之平均粒徑並無特別限定，就電子零件構裝用接著劑之透明性、流動性、接合可靠性等觀點而言，較佳為0.01~1μm左右。
上述無機填料可單獨使用，亦可混合多種無機填料而使用。
上述無機填料之含量並無特別限定，電子零件構裝用接著劑中之較佳之下限為10重量%，較佳之上限為70重量%。若上述含量未達10重量%，則存在電子零件構裝用接著劑之硬化物之強度或接合可靠性降低之情況。若上述含量超過70重量%，則存在電子零件構裝用接著劑之製膜性降低之情況。上述含量之更佳之下限為20重量%，更佳之上限為60重量%。
本發明之電子零件構裝用接著劑較佳為進而含有具有(甲基)丙烯酸基之矽烷偶合劑。藉由含有具有(甲基)丙烯酸基之矽烷偶合劑，電子零件構裝用接著劑對由矽等構成之半導體晶圓或晶片之接著力提高，即便於回焊等嚴酷之熱濕條件下亦不會產生與半導體晶圓或晶片之接著界面處之剝離或封裝龜裂，而可獲得較高之接合可靠性。
作為上述具有(甲基)丙烯酸基之矽烷偶合劑，例如可列舉：3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷等。該等具有(甲基)丙烯酸基之矽烷偶合劑可單獨使用，亦可併用兩種以上。
上述具有(甲基)丙烯酸基之矽烷偶合劑之含量並無特別限定，電子零件構裝用接著劑中之較佳之下限為0.05重量%，較佳之上限為5重量%。若上述含量未達0.05重量%，則存在於回焊等嚴酷之熱濕條件下產生半導體晶圓或晶片與電子零件構裝用接著劑之接著界面處之剝離或封裝龜裂之情況。即便上述含量超過5重量%，亦不會對電子零件構裝用接著劑，之接著力及耐濕熱性之提高產生助益。上述含量之更佳之下限為0.1重量%，更佳之上限為3重量%。
本發明之電子零件構裝用接著劑亦可視需要進而含有稀釋劑、觸變賦予劑、溶劑、無機離子交換體、滲出防止劑、鈦酸酯系偶合劑、膠黏劑等密接性賦予劑、橡膠粒子等應力緩和劑等其他添加劑。
製造本發明之電子零件構裝用接著劑之方法並無特別限定，例如可列舉：於上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物、上述3 官能以上之多官能(甲基)丙烯酸酯化合物、及上述自由基聚合起始劑中視需要摻合特定量之其他成分並進行混合之方法等。
上述混合方法並無特別限定，例如可列舉使用勻相分散機、萬能混合機、班布里混合機、捏合機等之方法。
本發明之電子零件構裝用接著劑之用途並無特別限定，藉由用於倒裝晶片構裝，可於較短之構裝時間內抑制焊料流動且充分進行焊接，抑制空隙，亦可提高耐回焊性。其中，較佳為將具有由本發明之電子零件構裝用接著劑構成之接著劑層之倒裝晶片構裝用接著膜預先貼附於基板或半導體晶片，藉由加熱同時進行電極接合與接著劑之硬化而構裝半導體晶片。
又，具有由本發明之電子零件構裝用接著劑構成之接著劑層之倒裝晶片構裝用接著膜亦為本發明之一。本發明之電子零件構裝用接著劑之厚度並無特別限定，較佳之下限為5μm，較佳之上限為60μm，更佳之下限為10μm，更佳之上限為50μm。
製造本發明之倒裝晶片構裝用接著膜之方法並無特別限定，例如可列舉如下方法等：於上述側鏈具有(甲基)丙烯醯基之丙烯酸聚合物、上述3官能以上之多官能(甲基)丙烯酸酯化合物、及上述自由基聚合起始劑中視需要摻合特定量之其他成分與溶劑並進行混合，將所得之接著劑溶液塗佈於脫模膜上，並使其乾燥而製造膜。
根據本發明，可提供一種可於較短之構裝時間內抑制焊料流動且充分進行焊接、抑制空隙、耐回焊性亦優異之電子零件構裝用接著劑。 又，根據本發明，可提供一種含有該電子零件構裝用接著劑之倒裝晶片構裝用接著膜。
以下，揭示實施例對本發明進行更詳細說明，但本發明並不僅限定於該等實施例。
(實施例1~14、比較例1~4)
(1)接著膜之製作
使用表1所記載之材料(表1中，MMA意指甲基丙烯酸甲酯，BA意指丙烯酸丁酯，HEMA意指甲基丙烯酸羥基乙酯)。依照表2或3所記載之摻合組成，將各材料添加於作為溶劑之甲基乙基酮(MEK)中，使用勻相分散機進行攪拌混合，藉此製造接著劑溶液。使用敷料器將所得之接著劑溶液以乾燥後之厚度成為30μm之方式塗佈於脫模PET膜上，並將其乾燥，藉此製造接著膜。在使用之前，以脫模PET膜(保護膜)保護所得之接著劑層之表面。
(2)半導體封裝之製造
準備將前端部由焊料構成之凸塊以50μm間距形成為周緣狀(peripheral)之晶圓(WALTS-TEG MB50-0101JY，焊料熔點235℃，WALTS公司製造)。將接著膜之單面之保護膜剝離，使用真空貼合機(ATM-812M， Takatori公司製造)，於載置台溫度80℃、真空度100Pa下使接著膜貼合於晶圓之形成有凸塊之面。
將接著膜另一面之脫模PET膜剝離，於露出之接著劑面層疊研磨用保護膠帶(ELEP HOLDER BT3100P，日東電工公司製造)。繼而，使用研磨裝置(DFG8560，Disco公司製造)，將晶圓之背面研磨至厚度成為100μm。於晶圓之經研磨之面貼附切晶帶，將研磨用保護膠帶剝離。其後，使用切晶裝置(DFD651，Disco公司製造)，以進給速度20mm/秒對晶圓進行切割，從而獲得附著有厚度為30μm之接著劑層之附有接著劑層之半導體晶片(7.6mm×7.6mm)。
準備具有Ni/Au電極之基板(WALTS-KIT MB50-0101JY，WALTS公司製造)。使用倒裝晶片接合機(FC-3000，TORAY ENGINEERING公司製造)，於焊接台溫度100℃之條件下，以120℃接觸，歷經2秒升溫至280℃，於280℃、0.8MPa下施加2秒荷重，將所得之附有接著劑層之半導體晶片熱壓接於基板上。其後，藉由於常壓、190℃於烘箱中保持30分鐘，使接著劑層完全硬化，從而獲得半導體封裝。
<評價>
對實施例、比較例中獲得之半導體封裝進行以下評價。將結果示於表2或3。
(1)焊料流動
藉由X射線透過裝置(MF100C，Hitachi Engineering & Services公司製造)觀察半導體封裝之焊接部，確認有無焊料流動。將焊料僅存在於焊接部之情形評價為良品(○)，將接合時被擠壓流動之焊料呈島狀存在於焊接部以 外之部位之情形評價為不良品(×)。
(2)焊接性
使用研磨機對半導體封裝進行剖面研磨，使用顯微鏡觀察焊接部之接合狀態。將上下電極間未嵌入樹脂(接著劑)、亦不存在因焊料流動引起之焊料流失、接合狀態良好之情形評價為良品(○)，將上下電極間嵌入少許樹脂(接著劑)、但不存在因焊料流動引起之焊料流失、接合狀態相對良好之情形評價為良品(△)，將上下電極間嵌入樹脂(接著劑)或存在因焊料流動引起之焊料流失、上下電極完全未接合之情形評價為不良品(×)。
(3)空隙評價
使用超音波探測影像裝置(C-SAM D9500，Nippon BARNES公司製造)觀察半導體封裝，對空隙之有無進行評價。將相對於半導體晶片之接著面積之空隙產生部分之面積未達0.5%之情形評價為良品(○)，將相對於半導體晶片之接著面積之空隙產生部分之面積為0.5%以上且未達1%之情形評價為良品(△)，將相對於半導體晶片之接著面積之空隙產生部分之面積為1%以上之情形評價為不良品(×)。再者，為良品抑或不良品之判斷係將n數設為5個，對相對於半導體晶片之接著面積之空隙產生部分之面積最小之半導體封裝進行評價。
(4)耐回焊試驗
將半導體封裝於85℃、60RH%下放置168小時而使其吸濕後，使其通過回焊爐(預熱150℃×100秒，回焊[最高溫度260℃])4次。將n數設為20個，確認產生半導體晶片自基板剝離之半導體封裝之個數。將20個半導體封裝中產生剝離之半導體封裝為0個之情形評價為○，將為1~3個之情 形評價為△，將為4~20個之情形評價為×。
Figure 104106575-A0202-12-0020-2
Figure 104106575-A0202-12-0021-3
Figure 104106575-A0202-12-0022-4
[產業上之可利用性]
根據本發明，可提供一種可於較短之構裝時間內抑制焊料流動且充分進行焊接、抑制空隙、耐回焊性亦優異之電子零件構裝用接著劑。又，根據本發明，可提供一種含有該電子零件構裝用接著劑之倒裝晶片構裝用接著膜。

Claims (7)

  1. 一種電子零件構裝用接著劑，其含有：側鏈具有(甲基)丙烯醯基之雙鍵當量1~5meq/g之丙烯酸聚合物、3官能以上之多官能(甲基)丙烯酸酯化合物、及自由基聚合起始劑，且其進而含有環氧樹脂與環氧硬化劑。
  2. 如申請專利範圍第1項之電子零件構裝用接著劑，其中，自由基聚合起始劑係熱自由基聚合起始劑。
  3. 如申請專利範圍第1或2項之電子零件構裝用接著劑，其中，環氧樹脂含有：1分子中具有環氧基與(甲基)丙烯醯基之環氧化合物。
  4. 如申請專利範圍第1或2項之電子零件構裝用接著劑，其進而含有無機填料。
  5. 如申請專利範圍第1或2項之電子零件構裝用接著劑，其進而含有具有(甲基)丙烯酸基之矽烷偶合劑。
  6. 如申請專利範圍第1或2項之電子零件構裝用接著劑，其中，側鏈具有(甲基)丙烯醯基之雙鍵當量1~5meq/g之丙烯酸聚合物僅於側鏈具有(甲基)丙烯醯基。
  7. 一種倒裝晶片構裝用接著膜，其具有：由申請專利範圍第1、2、3、4、5或6項之電子零件構裝用接著劑構成之接著劑層。
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